Spray composition



Patented July 16, 1940 SPRAY COMPOSITION Gerald H. Coleman, Midland,Mich, assignor to The Dow Chemical Company, Midland, Mich., acorporation of Michigan No Drawing. Application June 16, 1939, SerialNo. 279,467

12 Claims.

This invention concerns compositions particularly adapted for combatingflies, mosquitoes, moths, and similar insects.

Petroleum-distillate sprays containing extracts of such insecticidalplant products of pyrethrum flowers, derris, cube, barbasco, and thelike, are widely used for the control of household insect pests.Pyrethrin-containing sprays have a quick paralyzing action on flies butgenerally speaking the kill obtained thereby is low compared to thepercentage knockdown. Rotenonecontaining compositions give a morepermanent control but are relatively slow in their action, requiring aconsiderable period of time to kill insect pests contacted therewith.Both of the above-mentioned toxicants also suffer from the disadvantagethat they are unstable to heat, air, and light, and upon storage losetheir effectiveness to a considerable degree.

I have discovered that when a small amount of an allyl or 2-chloro-allylether of a phenol is 7 added to solutions of such toxicants as thepyrethrins and rotenone, improved spray compositions are obtained whichare more stable toheat and light and have a greater paralyzing effectand greater lethal effect against insects than the originalextract-containing compositions. These sprays give a kill against flies,for example, which more closely approximates the percentage knockdown ofsuch pests than do common household insect sprays heretofore employed.Furthermore, the allyl and 2-chloro-allyl ethers of phenols may besubstituted for the extracts of insecticidal plant products in spraycompositions. The resulting solutions compare favorably in toxic 'eflectwith those of the plant extracts and have the added advantage of beingsubstantially colorless and odorless and being relatively stable toheat, light, and air.

When the allyl or 2-chloro-allyl ether is used alone as the toxicant inan insect spray composition, a concentration from about 2 to about 10per cent in an inert organic solvent is suitable. For use in stabilizingand/or fortifying pyrethrinor rotenone-containing spray compositions,the allyl or 2-chloro-allyl ether is preferably employed in amount offrom about 0.2 to 3 grams per 100 milliliters of the spray solution.

The ethers I have found particularly valuable as insecticidal toxicantsand stabilizers for pyrethrinand rotenone-containing spray compositionsare those having the formula R-O-X wherein R represents an aromaticradical and X is allyl or 2-chloro-allyl. These compounds may beprepared by heating a mixture of. a phenol,

alcohol, caustic, and allyl or 2-chloro-allyl chloride to arefluxingtemperature, usually between and C. Following completion of the reactionthe ethereal reaction product may be distilled to remove alcohol, thenextracted with 5 ethyl ether, benzene, or other water-immiscible organicsolvent, and the extract fractionally distilled under reduced pressureto obtain the desired allyl or 2-chloro-allyl ether in substantiallypure form. While any suitable amounts of the phenol and allyl or2-chloro-allyl chlorides may be reacted together, equimolecularproportions have been found to give the desired ether compounds in goodyield. My co-pending application Serial No. 242,281, filed November 24,1938, discloses the preparation and properties of a number of thesecompounds. The allyl and 2-chloroallyl ethers falling within the scopeof the above formula have been found to be substantially odorless,colorless, and comparatively innocuous as regards human beings andwarm-blooded animals. Particularly advantageous is the fact that they donot appear to cause irritation and dermatitis upon contact with livingtissue and skin.

The method employed in determining the insecticidal toxicities ofsolutions of the above compounds and combinations thereof withpyrethrins and rotenone is substantially that described in Soap, 8, No.4 (1932), and known as the Feet-Grady method. The terms per cent andpercentage" as employed in the specification and claims with referenceto the composition of various spray materials refer to grams per 100milliliters thereof unless otherwise specified. For purpose ofcomparison in the examples, a control pyrethrin solution was employedconsisting of the extract of the toxic principles from 1 pound ofpyrethrum flowers dissolved in 1 U. S. gallon of a petroleum distillatehaving a boiling range of 345508 F. and a flash point of 137 F.

The invention is illustrated by the following examples:

Example 1 Percent knockdown in 10 minutes Percent mortality Compound in48 hours Pyrethrin control solution lllllllllllllll Allyl ether of2-chloro-4-phenylphenol (B. P. 158-l6l C. at, 3 mm. pressure) Allylether of 4-phenylphenol (melting at 79-80C.) l l l l. 87 50 Allyl etherof 2-hromo-4-phenylphenol (B. P. l65l68 C. at 3 mm. pressure). 54 35Allyl ether of fi-chloro-Z-phonylphenol (B. P. l38l4l C. at 2 mm.pressure) 35 2-chloro-allyl ether of 4-phenylphenol (melting at 75760.)... 91 57 2-chloro-allyl ether of 4-oyclo-hexyl phenol (B. P. l60l63C. at 4 mm. pressure)... 81 36 2-chloro-allyl ether of4-tertiary-butyl-phenol (B. P. l20-122 C. at 5 mm. pressure). 71 30Example 2 One gram of the allyl ether of 4-phenylphenol and 50milliliters of the pyrethrin control solution were mixed together anddiluted with an additional 50 milliliters of the petroleum distillatedescribed above. This spray material was compared with a 50 per centdilution of the control solution to determine the resistance of the twosprays to decomposition upon exposure to air, heat, and light. Thediluted control solution showed a knockdown of 95 per cent in 10 minutesand a kill of 2'7 per cent in 48 hours. The mixture of control solution,allyl ether of 4-phenylphenol, and petroleum distillate gave apercentage knockdown of 96 in 10 minutes and a percentage kill of 48 in48 hours. These compositions were then exposed for 72 hours to the raysof a mercury vapor lamp in a standard fadeometer at a constanttemperature of 57 C. The light employed had an intensity of 4000footcandles. Following this exposure, both samples were cooled to roomtemperature and retested according to the Feet-Grady methodsubstantially as described above. The observed toxicities for thediluted control solution were found to be 87 per cent knockdown in 10minutes and 1'! per cent kill in 48 hours. The percentage knockdown in10 minutes and killin 48hours for the composition comprising the allylether were 94 and 44, respectively.

It is evident from the foregoing that the solution of pyrethrum extractwas decomposed by the exposure to ultra-voilet light so as to be 37 percent less effective with respect to kill against houseflies. A similarsolution fortified and stabilized with the allyl ether compound showed adecrease in efiiciency of less than 9 per cent wit respect to kill uponsimilar treatment.

Example 3 2-chloro-allyl ether of 4-phenylphenol was substituted for thecorresponding allyl other as disclosed in Example 2 in the preparationof a fortified and stabilized pyrethrin spray. The initial toxicity ofthe pyrethrin solution alone when tested according to the Feet-Gradymethod was 27 per cent k l in 48 hours. The initial kill observed withthe composition containing the 2-chloroallyl ether of 4-phen'ylphenolwas 40 per cent in 48 hours. These two spray compositions were exposedin the fadeometer to ultra-violet rays substantially as described, for aperiod of 24 hours, cooled to room temperature and retested. Thepyrethrin solution was found to have decreased in effectiveness so as togive a kill of only 18 per cent in 48 hours. The spray containing the2-chloro-allyl ether and pyrethrin when similarly tested gave a kill of38 per cent. The reduction in toxicity shown by the pyrethrin solutionwas 33 per cent while that shown by the composition comprising the2-chloro-allyl ether was 5 per cent.

By substituting other allyl and 2-ch1oro-allyl ethers for thosedisclosed in the foregoing examples, insecticidal compositions may beobtained of comparable efliciency in the control of household andrelated insect pests. Representative of such com-pounds are allyl etherof 4-tertiarybutyI-Z-phenylphenol, boiling at -153 C. at 2 millimeterspressure; allyl ether of chloro-Z- cyclohexyl phenol, boiling at l30-132C. at 3 millimeters pressure; allyl ether of 2-phenylphenol, boiling at129-131 C. at 3 millimeters pressure; allyl ether of4-chloro-2-phenylphenol, boiling at l42-145 C. at 3 millimeterspressure; allyl ether of 4-tertiary-butyl phenol, boiling at 10'7-109 C.at 3.5 millimeters pressure; allyl ether of ortho-cresol; allyl ether of2.4-dichlorophenol; allyl ether of 2.4.6-tribromophenol; allyl ether of4-benzyl phenol; allyl ether of 2-chloro- 4-benzyl phenol; allyl etherof 2-aceto-phenol; allyl ether of 4-tertiary-amyl phenol; allyl ether of4-tertiary-octyl phenol; allyl ether of naphthol; allyl ether ofphenanthrol; allyl ether of 4-octadecanyl phenol; 2-chloro-allyl etherof phenol, boiling at 108-110 C. at 20 millimeters pressure;Z-chloro-allyl ethers of mixed isomericdimethyl phenols boiling at123-125 C. at 10 millimeters pressure; 2-chloro-allyl ether of2.4.6-trichlorophenol, freezing at 34 C.; 2- chloro-allyl ether of2-chloro-4-tertiary-butyl phenol, boiling at 134-137 C. at 3 millimeterspressure; 2-chloro-allyl ether of 2-phenylphenol boiling at 136-137 C.at 2 millimeters pressure; 2-chloro-allyl ether of carvacrol;2-chloro-allyl ether of thymol; Z-chloro-allyl ether ofmetaphenylphenol; 2-chloro-allyl ether of 4-benzyl phenol;Z-chloro-allyl ether of 4-methyl naphthol; 2-chloro-allyl ether of2.4-dinitro-phenol; 2-chloro-allyl ether of 4-phenylethyl phenol; 2chloro-allyl ether of 4-amino-phenol; 2-chloroallyl of naphthol; etc.

Mixtures of the above compounds may be dissolved in suitable solvents toobtain liquid spray materials having desirable characteristics asregards insecticidal toxicities, percentage of knockdown and kill, andstability to light and heat. Likewise, the allyl and 2-chloro-allylethers of phenols may be employed as stabilizers with extracts ofderris, cube, barbasco, and other insecticidal plant products. Besidepetroleum distillates other organic solvents such as benzene, ethylenechloride, hydrogenated naphthalene, butyl alcohol, etc., may be employedprovided only that such solvents be inert with respect to the toxicantsemployed, capable of dissolving the insecticidal plant products and/orallyl or 2- chloro-allyl ethers in the required amounts, andnon-corrosive in the sense that they be noninjurious to the skin andgeneral health of humans.

Other modes of applying the principle of my invention may be employedinstead of those explained, change being made as regards the materialsor the amounts thereof employed, provided the compositions defined byany of the following claims or their equivalent be employed.

I therefore particularly point out and distinctproduct selected from theclass consisting of the extracts of pyrethrinand rotenone-bearing plantsand as an added toxicant and stabilizer a compound having theformulaR.OX wherein R represents an aromatic radical and X is selected from thegroup consisting of the allyl and 2-.chloro-allyl radicals.

3. An insecticidal spray comprising a non-cor rosive organic solventhaving dissolved therein an extract of a pyrethrin bearing plant and asan added toxicant and stabilizer a compound having the formula Rr-O-Xwherein R represents an aromatic radical and X is selected from thegroup consisting of the allyl and 2-chloro-allyl radicals.

4. An insecticidal spray comprising a, non-corrosive organic solventhaving dissolved therein as an active toxicant a compound having theformula ROCH2-CH,=CI-Iz wherein R represents an aromatic radical.

5. An insecticidal spray comprising a non-corrosive organic solventhaving dissolved therein as an active toxicant a compound having theformula ROCH2-CC1=CH2 wherein R represents an aromatic radical.

6. An insecticidal spray comprising a non-corrosive organic solventhaving dissolved therein as an active toxicant a compound having theformula R-O-X wherein R represents an aromatic radical, and X isselected from the group consisting of the allyl and \Z-ehloro-allylradicals, in amount ranging between 9.2 and 10 gr per millilitersthereof; I

7. An insecticidal spray comprising a non-cor rosive organic solventhaving dissolved therein as an active toxicant a compoundhavingthdfurmula R-O-X wherein it represents a halogensubstitutedaromatic radical and X is selected from the group consisting of theallyl and 2- chloro-allyl radicals.

8. An insecticidal spray comprising a nonworrosive organic solventhaving dissolved therein as an active toxicant a compound having theformula wherein X is selected from the group consisting of the allyl andZ-ehloro-allyl radicals, Y represents a hydrocarbon radical, Zrepresents a member of the group consisting of hydrogen and thehydrocarbon radicals, and n is an integer not greater than 3. I

9. An insecticidal spray comprising a non-corrosive organic, solventhaving dissolved therein as an active toxicant a compound having theformula wherein X is selected from the group consisting of the allyl and2-chloro-allyl radicals.

10. An insecticidal spray comprising a mom corrosive organic solventhaving dissolved there- 'inas an active toxicant the allyl ether of &-

12. An insecticidal spray comprising a noncorrosive organic solventhaving dissolved therein as an active toxicant the allyl ether of2-chloro-4-tertiary-butyl phenol.

, I GERALD H. COLEMAN.

